Process for the manufacture of sulpho-alkylesters of fatty acids



y 1958 H. GUSHIN ET AL 2,844,607

PROCESS F OR THE MANUFACTURE OF SULPHOALKYLESTERS OF FATTY ACIDS Filed Aug. 9, 1956 6 full [/8 7 5 7 I /4' f5 [4 I I I I I 1 i Fig. 2.

INVENTOR. I I

PROCESS FOR THE MANUFACTURE OF SULPHO- ALKYLESTERS F FATTY ACIDS Harold Gushin and Frederick J. Zelman, Roselle, N. L, assignors to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware Application August 9, 1956, Serial No. 603,086

Claims. (Cl. 260-400) The invention here presented is a new process for the preparation of sulphoalkylesters of fatty acids, in which a stream of reaction mixture in the form of a coarse slurry is delivered to a centrifugal reactor in which the reaction material is thrown violently against a heated cylindrical wall and maintained in turbulent flow along that wall by a rapidly rotating vane system whereby sufficient turbulence is obtained to dislodge the reaction product from the surface of the reactor, and simultaneously to apply to the solid particles in the slurry, a substantial amount of attrition which breaks up the slurry particles and dislodges a reaction film from the surface, the combined effect being to give a very rapid reaction while highly accurate temperature control is maintained and a steady uniform throughput is obtained to yield a very rapid reaction with a sharp reduction in side reactions, a higher reaction efiiciency and a very significantly lower cost.

There has been need for a variety of substances, used as intermediates for dyestuffs, pharmaceuticals and the like, which are best prepared by a reaction of sodiumisethionate with a fatty acid halide as well as other similar reactions. In the past these reactions have been carried out batchwise after a very thorough grinding of the solid components of the reaction. A very substantial improvement in this reaction has been obtained by the procedure shown in the copending application of H. H. Tiedemann, Serial 460,438, filed October 5, 1954, by which the reaction mixture is prepared by grinding the organic acid salt of a reactive metal into a very fine powder, slurrying the powder with a carboxylic acid chloride to form a homo geneous slurry, and conducting the reaction on a heated metallic surface such as a drum-drier. This procedure yields a very excellent product and is a very satisfactory method of conducting the reaction, but it has the disadvantage that the solid reactant must be very finely powdered, and'the reaction on the drum-drier is slow, thereby involving relatively high costs.

According to the present invention it is now found that if the reaction is conducted in a device having the form of a heated cylinder with a set of rapidly rotating vanes therein, the edges of which have a relatively small clearance from the heated cylinder, together with means for providing a rapid rotation of the vane system and means for the delivery to and discharge from the device of materials in the form of a mixture or slurry in which it is desired to cause a reaction;'such devices being available on the market under such names as Turba-Film Evaporator or Roto-Vak or Adjusto-Film or the like, as shown in the drawing, in which a central vertical shaft is equipped with vanes and positioned inside of a heated cylinder; the device being equipped with an inlet duct a short distance below the top of the rotor, and an outlet duct at the bottom, below the rotor, a highly efficient system is obtained. Accordingly the reaction components are mixed, without special grinding or pulverizing to yield a coarse slurry which is delivered through the input duct to the rotor, caught by the vanes of the rotor and thrown 2,844,607 Patented July 22, 1958 violently against the heated cylindrical wall, then caught again by the edges of the rotor and brought into a condition of violent turbulence as the material flows slowly along the heated cylindrical wall. Theresult is a rapid reaction on the surfaces of the granules in the slurry and dislodgment of the reaction product from the surface of the granules, making available fresh reaction surface. The reaction material forms a highly turbulent film on the inner surface of the heated wall which however is so thin that no hot spots appear, and accordingly the reaction does not overheat but is held strictly at the desired reaction temperature. In addition, the spinning blades of the rotor keep the film on the surface in violent turbulence and keep it from building up anything thicker than the clearance distance between the edges of the rotor blades and the wall. This clearance may, if desired, be made less than the average particle size in the slurry with the result that the slurry particles are subjected to intensive attrition during the reaction, making unnecessaryv any grinding or special subdivision, since the reaction occurs on the surface of the solid particles and the reactionv forms, a procedure possible in no other known device. Accordingly the completed reaction product is delivered from the bottom outlet, the total amount of reaction ma-- terial in the reactor is very small, ranging from a few ounces to a small number of pounds, the throughput rate: is very high, and the reaction is carried to completion. within the reactor, and little or no unreacted material escapes from the bottom outlet.

Thus the process of the present invention mixes together two reactants, one of which is fluid or can be made fluid. by a suitable heating procedure, the other of which is solid at the reaction temperature, passes them over a heated wall in the presence of a rapidly rotating member. which produces a violent turbulence in a film of reactant material on the heated wall, whereby a rapid reaction is obtained, hot spots are prevented, the necessity for fine:

grinding is obviated and a complete, highly efficient economical combination and reaction is obtained. Other objects and details of the invention will be apparent from the following description when read in connection with the accompanying drawings, wherein Figure 1 is a view in vertical elevation, partly in sec--.

tion of the reactor member of the present invention, and

Figure 2 is a diagrammatic showing of the complete processing apparatus.

Referring to Figure 1, the reactor of the present invention consists of a vertical cylindrical member 1, having a jacket member 2 to form a steam jacket around the member 1. The member 1 is closed at the bottom by a conical member 3 having an outlet connection 4. The top of the member 1 is expanded into a chamber 5 Within which are positioned stationary baflle members 6 carried upon a collar member 7 attached to the surface of the chamber 5.

Within the member 1 and member 5 there is then positioned a rotor member 8 made up of a central shaft 9 and blade members 11. The chamber 5 is closed at the top by a header member 12. An inlet member 14 is provided leading into the member 1, which is below the enlargement which forms the chamber 5. A vapor outlet member 15 is provided at the top of the chamber member 5 and the shaft 9 is extended upward from a packing gland member (not shown) and a pulley member 16 is mounted upon the upper end of the shaft 9 for driving by a belt 1'7 from a motor (not shown) the rotor 8 is preferably driven at a speed within the range between about 400 R. P. M. and 2000 R. P. M. t

Referring to Figure 2, there is provided a container 18.

for the reception of a reactant, and a second container 19 for a second reactant. These reactants may be both solids, or'both liquids, or preferably one a solid and the-other a liquid. Discharge ducts from the containers 18 and 19 are led to a mixer member 21 which may take any convenient form, which will makea reasonably of the twd'components. 'It mavtake the fdrm merely o f'a paddle'niixer'or a' container having a propellerflstirrer, .or an anchor stirrer, or may be a Werner-Pfieiderer kneader as desired, or as required by the physicalcondition of the reactantmaterials. It is however desirable that the mixture should flow, either by virtue of fluidity mar least oneof the components (or by virtue of the presence of a fluid diluent), or that both particlesbe pulverulent, so that they will flow like dry sand. The discharge 'from'the mixerll is then conveyed by. a pump, or other conveyer member 22 through a duct 2 3 tothe input 1 4 of the reactor. The reaction mixturethen is heated by the steam within the jacket =2 and the reaction'occurs'as the material flows downward along the inside of the member 1 to the cone 3-and discharge 4. Fromthe discharge 4 the material is carried by a duct member 23d to a receptacle 24 in which the reaction mixture may be cooled or other treatment given to it,as;desired,-including such procedures as flirther reaction, pulverizing, granulating, cooling and the 1i Ahighlydesirable and advantageous reaction may be conducted in this device for the preparation'of esters of ea'rboxylic acid chlorides with Z-hydroxyalkahe sulfonic acid salts of alkali metals and the like. For this purpose sodium-isethionate in'coar sely pulverized form may be 'delivered to the container 18 and"a suitable fatty acid halide may be delivered to the container 19, the two being delivered inappropriate proportions through a suitable proportioning device 25 to-thernixer 21 where they are roughly mixed. The mixture; is then delivered through theduct 23 to the'input 14 of the reactor 1. Rotation of the blades llthrows the slurry of sodium-isethionate in fatty acid halide against the heated wall member 1 where it is promptly brought up to the reaction temperature as setby the material in the jacket 2 which may be steam under appropriate pressure or may be hot water or Dowtherm or may be molten lead or any other fluid heating material which will give the desired temperature. Usually anf elevated temperature'is required, but lower temperatures, as obtainedby refrigeration, are not excluded. The strong centrifugal force developed by the spinning blades 11 throws the solid portion of the slurry against the wall member 1 and elfects' immediately a substantial reduction in particle size. At the same time reaction occurs on the surface of the particles to yield a reaction product having different physical properties, suflicient to permit the breaking away of the reaction product from the particle surface. The small clearaneebetween the spinning blades 11 and the heated wall 1 results in a very high turbulence in the film on themember 1, the film being" partly dragged around the wall by force developed by' the blades, and partlycarried downward in a spiral path by gravity. However the rapid motion of the blades 1 yields a violent turbulence in the film-of the active material on the wall 1, resulting in an extremely good mixing of the reactants and a rapid removal of the reaction product from the surface of the solid particles. The rate of delivery-of the reaction mixture to the input duct 14 determines -in la rge measure the rate at which the material flows downward, a heavy ':Si1'81'l'l givinga more rapid downward flow than'a small stream. If the reactant materials are .in the form of a fine grain slurry so that the reaction proceeds rapidly, the clearance between the vanes 11 and the 'wall 1 maybe made relatively great, andfa rapid flow occurs. :If the reaction is slow, or if the reaction lproductlis slow to part from the slurry particles, then asmaller stream may be used and a slower reaction obtained. Also the reaction time maybe in considerable measure controlled by the length of the member 1, a shortdength giving a shorter react-ion time.

The following examples are odered as showing the best known process for practising the invention; not as imposing limitations upon the claims solicited.

Example 1 Into container 18 charge 10 lbs. of sodium-isethionate. Into container 19 charge 16'. lbs. of coconut fatty acid chloride.

These are then proportioned through device 25 into mixer 21. The slurry from 'mixer 21 is fed through pump 22 at the rate of lbs. per hour to the Turba- Film which has 8.5 square feet of wall surface.

The Turba-Film is heated by steam (55 lbs. per square inch in the jacket) andthe rotor blades are turning at 720 R. P. M. The product is collected in chamber 24.

Yield: 24 lbs. of product.

A considerable number of runs, according to the above stated example, were made varying the temperature in the jacket, the rate of feed and the rotor speed. These subsequent tests showedthat there was no significant difference betweenthe various temperatures within the range between about 240 F. and 350 F. Similarly the series of tests showed that there were no significant diiferences produced by'difierences in'rotor speed between about 720 and 1100 R.-P. .M. Sirnilarlythere were no significant difierenccs in the amount of unreacted material between a very small stream of reactantsand a stream as large as the reactor would handle; there being a substantially complete reactionwith all rates of feed,sup to the point where the amount of material in the rotor was so great as to require an undue powerinput.

.The above indicated tests were made using sodiumisethionate and a coconut fatty acid chloride as the reactants. However the reaction is equally elfeetive with any of the fatty acid chlorides, without regard to the molecular weight, or carbon atommembertherein. Thus the reaction proceeds with acetal chloride in which there are 2' carbon atoms inthe carbon atom chain, and it proceeds equally well with stearic acid chloride having 18 carbon atoms in the chain. The reaction proceeds equally well with any, of the intervening carbon atom chain members. Similarly the reaction proceeds equally WelLwith oleic acid chloride.

The reaction is ,most satisfactory when at least one of the reactants is liquid, or melts at thereaction temperature. In some instances a satisfactory reaction between 2 solids is obtained, but usually if both reactants are solid at the reaction temperature it is desirable that an inert carrier liquid be added to the reaction mixture.

Thus by the present, invention there is produced a new and valuable method for conducting an economical reactio vw ic a react ntm x ur r u ry is c n e to a vertical cylinder containing rotating blades with close clearance from the cylinder wall, thrown againstthe cylinder wall and film formed thereon and maintained in violent turbulence on that wall while carried downwards in thin filmby gravitation, whereby, ;very accurate temperature control is obtained,.hot,spots are avoided and a rapid reaction obtained by virtue of the violent turbulence which gives a highly intimate mixing of the reactants and dislodges reaction product from'solid grains in a slurry.

VVhilethere are above disclosed but a limited number of embodiments of the device and process of the present invention it is possible to providestill other embodiments without departingfromthe inventive conceptherein disclosed, audit is therefore desired that only suchlimitations be imposed upon theappended claimsas are, stated therein or required bythe prior art.

The invention claimed is:

1. Process for the production of sultoethylesters of fatty acids, which comprises forming a slurry bymixing together dry sodium-isethionate in coursely pulverized form with a. fatty acid halide, delivering s aid slurry to a suriace heatedto an elevated temperature swept by rapidly moving members so as to produce a thin film of reaction product on said heated surface and simultaneously causing attrition of said film by violent turbulence efiected by the said rapidly moving members, the turbulence and temperature being maintained until the reaction between the sodium-isethionate and the fatty acid halide is substantially complete, the attrition being utilized to separate the reaction product from said surface.

2. Process for the production of sulfoethylesters of fatty acids, which comprises forming a slurry by mixing together dry sodium-isethionate in coursely pulverized form with a fatty acid halide, delivering said slurry with force to a surface heated to an elevated temperature swept by rapidly moving members so as to produce a thin film of reaction product on said heated surface and simultaneously causing attrition of said film by violent turbulence efiected by the said rapidly moving members, the turbulence and temperature being maintained until the reaction between the sodium-isethionate and the fatty acid halide is substantially complete, the attrition being utilized to separate the reaction product from said surface.

3. Process for the production of sulfoethylesters of fatty acids, which comprises forming a slurry by mixing together dry sodium-isethionate in coursely pulverized form with a fatty acid halide, delivering said slurry with force to a surface heated to a temperature of 240 F. to 350 F. swept by rapidly moving members so as to produce a thin film of reaction product on said heated surface and simultaneously causing attrition of said film by violent turbulence effected by the said rapidly moving members, the turbulence and temperature being maintained until the reaction between the sodium-isethionate and the fatty acid halide is substantially complete, the attrition being utilized to separate the reaction product from said surface.

4. Process for the production of sulfoethylesters of fatty acids, which comprises forming a slurry by mixing together dry sodium-isethionate in coursely pulverized form with a fatty acid chloride, delivering said slurry with force to a surface heated to a temperature of 240 F. to 350 F. swept by rapidly moving members so as to produce a thin film of reaction product on said heated surface and simultaneously causing attrition of said film by violent turbulence efiected by said rapidly moving members, the turbulence and temperature being maintained until the reaction between the sodium-isethionate and the fatty acid chloride is substantially complete, the attrition being utilized to separate the reaction product from said surface.

5. Process for the production of sulfoethylesters of fatty acids, which comprises forming a slurry by mixing together 10 parts by weight of dry sodium-isethionate in coursely pulverized form with 16 parts by weight of coconut fatty acid chloride, delivering said slurry with force to a surface heated to a temperature of 240 F. to 350 F. swept by rapidly moving members so as to produce a thin film of reaction product on said heated surface and simultaneously causing attrition of said film by violent turbulence effected by the said rapidly moving members, the turbulence and temperature being maintained until the reaction between the sodium-isethionate and the fatty acid chloride is substantially complete, the attrition being utilized to separate the reaction product from said surface.

References Cited in the file of this patent UNITED STATES PATENTS Re. 23,823 Molteni May 4, 1954 1,881,172 Daimler et al Oct. 4, 1932 2,129,896 Whiteman Sept. 13, 1938 2,130,362 Muncie Sept. 20, 1938 2,697,031 Hervert Dec. 14, 1954 

1. PROCESS FOR THE PRODUCTION OF SULFOETHYLESTERS OF FATTY ACIDS, WHICH COMPRISES FORMING A SLURRY BY MIXING TOGETHER DRY SODIUM-ISETHIONATE IN COURSELY PULVERIZED FORM WITH A FATTY ACID HALIDE, DELIVERING SAID SLURRY TO A SURFACE HEATED TO AN ELEVATED TEMPERATURE SWEPT BY RAPIDLY MOVING MEMBERS SO AS TO PRODUCE A THIN FILM OF REACTION PRODUCT ON SAID HEATED SURFACE AND SIMULTANEOUSLY CAUSING ATTRITION OF SAID FILM BY VIOLENT TURBULENCE EFFECTED BY THE SAID RAPIDLY MOVING MEMBERS, THE TURBULENCE AND TEMPERATURE BEING MAINTAINED UNTIL THE REACTION BETWEEN THE SODIUM-ISETHIONATE AND THE FATTY ACID HALIDE IS SUBSTANTIALLY COMPLETE, THE ATTRITION BEING UTILIZED TO SEPARATE THE REACTION PRODUCT FROM SAID SURFACE. 